Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/48—Halides, with or without other cations besides aluminium
  • C01F7/50—Fluorides
  • C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
  • C01F7/788—Ammonium aluminium fluorides, e.g. ammonium hexafluoroaluminate
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

• This invention relates to a process for the preparation of ammonium tetrafluoroaluminate, particularly, from ammonium hexafluoroaluminate.
• Ammonium tetrafluoroaluminate is known as an industrially useful compound, e.g., for the preparation of aluminum fluoride.
• an aqueous solution of ammonium fluoride is caused to react with either aluminum oxide or aluminum hydroxide to form ammonium tetrafluoroaluminate either by keeping the reaction system under a reaction condition created by a combination of a considerably high pressure and an elevated temperature or by blowing steam through the reaction system.
• Industrial application of this process appears to be not particularly advantageous by reason of needing either a severe reaction condition or a large quantity of steam.
• a process of preparing ammonium tetrafluoroaluminate comprises the steps of preparing an aqueous slurry of ammonium hexafluoroaluminate and an aluminum compound selected from aluminum hydroxide and aluminum oxide, and adding an inorganic acid to the slurry to precipitate ammonium tetrafluoroaluminate.
• the precipitation occurs in a short time merely by keeping the reaction system under the atmospheric pressure at or somewhat above room temperature, more preferably at a temperature between 70° and 100° C.
• the inorganic acid is added preferably in such an amount that the pH of the mother liquor after completion of the reaction is in the range between 4.0 and 7.0.
• ammonium hexafluoroaluminate a starting material in a process according to the invention.
• This compound is usually prepared by adding either aluminum hydroxide or aluminum oxide to an aqueous solution of ammonium fluoride.
• an aluminum salt typified by aluminum sulfate may be added to the same solution.
• the former process is preferable since the reaction system containing therein solid phase ammonium hexaluoroaluminate can be used with no extra procedure as the aqueous slurry for producing ammonium tetrafluoroaluminate only if aluminum hydroxide or aluminum oxide is added initially in slight excess.
• ammonium hexafluoroaluminate is formed according to the equation (1):
• this reaction system under the described condition does not form ammonium tetrafluoroaluminate even if an increased amount of aluminum hydroxide is added to the aqueous solution so that the molar ratio of aluminum hydroxide to ammonium fluoride may become 1:4.
• the reaction in this case proceeds according to the equation (2) and gives an aqueous slurry containing a mixture of ammonium hexafluoroaluminate and unreacted aluminum hydroxide:
• the liberated ammonia is taken out of the reaction system either during the reaction or after completion of the reaction and recovered in the form of either ammonia gas or an aqueous ammonia solution.
• An analogous slurry and ammonia are produced also when aluminum oxide is used in place of aluminum hydroxide.
• the concentration of the thus obtained aqueous slurry is adjusted to a value ranging from 10 to 40% by weight, more preferably 15 to 30%, before the addition of an inorganic acid.
• useful inorganic acids are sulfuric acid, hydrochloric acid and nitric acid.
• the amount of aluminum hydroxide or aluminum oxide added to the initial solution of ammonium fluoride is preferably in the range between 95 and 105% of a calculated value on the assumption that ammonium tetrafluoroaluminate is formed.
• equation (3) aluminum hydroxide or aluminum oxide is added initially in a smaller amount so that the reaction of equation (1) may take place and supplemented after the formation of ammonium hexafluoroaluminate in an amount just sufficient for completing the reaction of typically the following equation (3):
• the inorganic acid is added to the slurry preferably in such an amount that the pH of the slurry after completion of the reaction of equation (3) is in the range between 4.0 and 7.0.
• the reaction of equation (3) occurs when the reaction system is kept at room temperature at the lowest, but the reaction system is preferably heated to a temperature of 70° to 100° C.
• ammonium hexafluoroaluminate as the starting material for a process according to the invention can be prepared from an aqueous solution of ammonium fluoride and aluminum sulfate by the processes disclosed in U.S. Pat. Nos. 2,981,597 and 3,501,268.
• a process according to the present invention is advantageous over conventional processes in that ammonium tetrafluoroaluminate of a remarkably high purity is obtained in quite a high yield by using only relatively inexpensive materials and that the process can be performed easily and completed in a short time.
• the particle size of the produced ammonium tetrafluoroaluminate can be controlled optionally in a process according to the invention.
• the particle size can be varied by adding the inorganic acid to the slurry in different manners. When the total amount of the acid is poured into the slurry at one time, the particle size of the crystalline ammonium tetrafluoroaluminate is in the range from about 10 to about 20 ⁇ m.
• the particle size increases to the ranges from about 20 to about 50 ⁇ m, and from about 50 to about 100 ⁇ m, when the acid is added intermittently and continuously in certain period of time, respectively.
• the aqueous slurry of ammonium hexafluoroaluminate and aluminum hydroxide was prepared according to Example 1, and 166 g of 35% hydrochloric acid was added to this slurry.
• the molar ratio of ammonium hexafluoroaluminate to hydrochloric acid (58 g., 1.59 mol.) was about 2:3.5.
• the resulting mixture was kept under the atmospheric pressure at 80° C. for 20 min with stirring. Then the solid component, which was crystalline ammonium tetrafluoroaluminate, was separated from the slurry by filtration.
• the thus obtained crystals weighed 162 g in all and individually had average particle sizes ranging from about 60 to about 70 ⁇ m.
• the fluorine concentration in the mother liquor was 0.19 Wt% and the pH was 5.5.
• the purity of the product was 99.1% and the yield based on F was 98.1%.
• the aqueous slurry of ammonium hexafluoroaluminate and aluminum hydroxide was again the same as in Example 1, and 161 g of 62% nitric acid was added to this slurry.
• the molar ratio of ammonium hexafluoroaluminate to nitric acid (100 g., 1.58 mol.) was about 2:3.5.
• the resulting mixture was kept under the atmospheric pressure at 30° C. for 120 min with stirring. After that, the solid component was separated from the slurry by filtration and identified as crystalline ammonium tetrafluoroaluminate.
• the crystals weighed 162 g in all and individually had average particle sizes ranging from about 50 to about 80 ⁇ m.
• the fluorine concentration in the mother liquor was 0.18 Wt% and the pH was 5.5.
• the purity of the product was 99.1% and the yield based on F was 98.2%.
• the aqueous slurry of ammonium hexafluoroaluminate and aluminum hydroxide prepared in Example 1 was kept at 80° C. for 20 min with stirring but without adding any inorganic acid. Substantially no reaction occurred in the slurry, and the formation of ammonium tetrafluoroaluminate was not recognized.
• Example 2 The same aqueous slurry as in Example 1 was put into an autoclave without addition of any inorganic acid and kept at 180° C. for 60 min with stirring. Then the C. system was cooled to 50° C in 60 min. The solid component was separated from the slurry by filtration and identified as a mixture, weighing 157 g in its entirety, of 93.6 Wt% of ammonium tetrafluoroaluminate, 5.1 Wt% of ammonium hexafluoroaluminate and 1.3 Wt% of aluminum hydroxide. The yield of ammonium tetrafluoroaluminate based on F was 94.4%.
• ammonium hexafluoroaluminate 644 g of 25% aqueous solution of aluminum sulfate was added to 557 g of 40% aqueous solution of ammonium fluoride (accordingly the weight ratio of Al 2 (SO 4 ) 3 to NH 4 F was 161 g : 223 g). A crystalline product separated out immediately. Then an aqueous ammonia solution was added to the resulting slurry, so that the pH of the slurry was maintained at 5 to 6. After completion of stirring for 30 min, the crystalline product was separated from the slurry by filtration followed by washing with water and drying. The product weighed 176 g and identified by X-ray analysis as substantially pure (NH 4 ) 3 AlF 6 . The yields based on F and Al were 90% and 96%, respectively.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Geology (AREA)
• Inorganic Chemistry (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Surface Treatment Of Glass (AREA)

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Citations (8)

• 1974
  • 1974-10-28 JP JP12346774A patent/JPS534080B2/ja not_active Expired
• 1975
  • 1975-10-23 FR FR7532494A patent/FR2289448A1/fr active Granted
  • 1975-10-24 US US05/625,476 patent/US4034068A/en not_active Expired - Lifetime
  • 1975-10-24 IT IT51913/75A patent/IT1048333B/it active
  • 1975-10-27 DE DE2547998A patent/DE2547998C3/de not_active Expired
  • 1975-10-28 GB GB4431975A patent/GB1463267A/en not_active Expired
  • 1975-10-28 BE BE161299A patent/BE834929A/xx not_active IP Right Cessation

Patent Citations (8)

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